Catalyst delivery method, a catalyst feeder and their use in a polymerization process

ABSTRACT

The present invention relates to an improved catalyst delivery method for introducing a supported bulky ligand metallocene-type catalyst system to a reactor for polymerizing one or more olefin(s). In particular, the invention provides for a method of introducing a supported metallocene-type catalyst system into a polymerization reactor by and in the presence of a carrier solution of an antistatic agent and a liquid diluent. Also, the invention is directed toward a catalyst feeder for use in a polymerization process.

FIELD OF THE INVENTION

[0001] The present invention relates to an improved catalyst deliverymethod for introducing a supported bulky ligand metallocene-typecatalyst system to a reactor for polymerizing one or more olefin(s).Also, the invention relates to an improved catalyst feeder forintroducing a catalyst into a polymerization reactor.

BACKGROUND OF THE INVENTION

[0002] The use of bulky ligand metallocene-type catalyst systems inpolymerization processes to produce a diverse array of new polymers foruse in a wide variety of applications and products is well known in theart. Typical bulky ligand metallocene-type compounds are generallydescribed as containing one or more ligands capable of η-5 bonding tothe transition metal atom, usually, cyclopentadienyl derived ligands ormoieties, in combination with a transition metal selected from Group 4,5 or 6 or from the lanthanide and actinide series of the Periodic Tableof Elements. Exemplary of the development of these and othermetallocene-type catalyst compounds and catalyst systems are describedin U.S. Pat. Nos. 5,017,714, 5,055,438, 5,096,867, 5,198,401, 5,229,478,5,264,405, 5,278,119, 5,324,800, 5,384,299, 5,408,017, 5,491,207 and5,621,126 all of which are herein fully incorporated by reference.

[0003] It is also well known that these bulky ligand metallocene-typecatalyst systems have a tendency toward fouling and/or sheeting,particularly when they are supported on a carrier, and especially whenused in a gas or slurry polymerization process.

[0004] For example, in a continuous slurry process fouling on the wallsof the reactor, which acts as heat transfer surface, can result in manyproblems. Poor heat transfer during polymerization can result in polymerparticles adhering to the walls of the reactor, where they can continueto polymerize. This can be detrimental to the process and can result inpremature reactor shutdown. Also, depending upon the reactor conditions,some of the polymer may dissolve in the reactor diluent and redeposit onfor example the metal heat exchanger surfaces.

[0005] In a continuous gas phase process for example, a continuousrecycle stream is employed. The recycle stream composition is heated bythe heat of polymerization, and in another part of the cycle, heat isremoved by a cooling system external to the reactor. Fouling in acontinuous gas phase process can lead to the ineffective operation ofvarious reactor systems. For example, the cooling system, temperatureprobes and the distributor plate, which are often employed in a gasphase fluidized bed polymerization process can be affected. These upsetscan lead to an early reactor shutdown.

[0006] Another major problem associated primarily with fluid bed gasphase operation involves “sheeting” in the reactor. This is particularlyproblematic with bulky ligand metallocene-type catalysts because oftheir very high activity on a per gram of metal basis that often resultsin the generation of extreme heat local to the growing polymer particle.Also, the polymer produced with these bulky ligand metallocene-typecatalysts are very tough, making the molten sheet that may form in thereactor difficult to break-up and remove from the reactor. Anotherproblem associated with using a supported bulky ligand metallocene-typecatalysts is that often there is a partial or complete pluggage of thecatalyst delivery tube used to introduce the supported catalyst into thereactor. This pluggage phenomenon is particularly a problem when usingvery high activity, a high comonomer incorporating supported bulkyligand metallocene-type catalyst system.

[0007] As a result of the reactor operability issues associated withusing supported bulky ligand metallocene-type catalysts and catalystsystems various techniques have been developed that are said to resultin improved operability.

[0008] For example, various supporting procedures or methods forproducing a metallocene-type catalyst system with reduced tendencies forfouling and better operability have been discussed in the art. U.S. Pat.No. 5,283,218 is directed towards the prepolymerization of a metallocenecatalyst. U.S. Pat. Nos. 5,332,706 and 5,473,028 have resorted to aparticular technique for forming a catalyst by “incipient impregnation”.U.S. Pat. Nos. 5,427,991 and 5,643,847 describe the chemical bonding ofnon-coordinating anionic activators to supports. U.S. Pat. No. 5,492,975discusses polymer bound metallocene-type catalyst systems. U.S. Pat. No.5,661,095 discusses supporting a metallocene-type catalyst on acopolymer of an olefin and an unsaturated silane. PCT publication WO97/06186 published Feb. 20, 1997 teaches removing inorganic and organicimpurities after formation of the metallocene-type catalyst itself. PCTpublication WO 97/15602 published May 1, 1997 discusses readilysupportable metal complexes. PCT publication WO 97/27224 published Jul.31, 1997 relates to forming a supported transition metal compound in thepresence of an unsaturated organic compound having at least one terminaldouble bond.

[0009] Others have discussed different process modifications forimproving operability with metallocene-type catalysts and conventionalZiegler-Natta catalysts. For example, PCT publication WO 97/14721published Apr. 24, 1997 discusses the suppression of fines that cancause sheeting by adding an inert hydrocarbon to the reactor. U.S. Pat.No. 5,627,243 discusses a new type of distributor plate for use influidized bed gas phase reactors. PCT publication WO 96/08520 discussesavoiding the introduction of a scavenger into the reactor. U.S. Pat. No.5,461,123 discusses using sound waves to reduce sheeting. U.S. Pat. No.5,066,736 and EP-A1 0 549 252 discuss the introduction of an activityretarder to the reactor to reduce agglomerates. U.S. Pat. No. 5,610,244relates to feeding make-up monomer directly into the reactor above thebed to avoid fouling and improve polymer quality. U.S. Pat. No.5,126,414 discusses including an oligomer removal system for reducingdistributor plate fouling and providing for polymers free of gels. EP 0453 116 A1 published Oct. 23, 1991 discusses the introduction ofantistatic agents to the reactor for reducing the amount of sheets andagglomerates. U.S. Pat. No. 4,012,574 discusses adding a surface-activecompound, a perfluorocarbon group to the reactor to reduce fouling. WO96/11961 published Apr. 26, 1996 discusses as a component of a supportedcatalyst system an antistatic agent for reducing fouling and sheeting ina gas, slurry or liquid pool polymerization process. U.S. Pat. No.5,026,795 discusses the addition of an antistatic agent with a liquidcarrier to the polymerization zone in the reactor. U.S. Pat. No.5,410,002 discusses using a conventional Ziegler-Nattatitanium/magnesium supported catalyst system where a selection ofantistatic agents are added to directly to the reactor to reducefouling. U.S. Pat. Nos. 5,034,480 and 5,034,481 discuss a reactionproduct of a conventional Ziegler-Natta titanium catalyst with anantistat to product ultrahigh molecular weight ethylene polymers.

[0010] There are various other known methods for improving operabilityincluding coating the polymerization equipment, injecting various agentsinto the reactor, controlling the polymerization rate, particularly onstart-up, and reconfiguring the reactor design.

[0011] While all these possible solutions might reduce fouling orsheeting somewhat, some are expensive to employ and/or may not reduceboth fouling and sheeting to a level sufficient for the successfuloperation of a continuous process, particularly in a commercial orlarge-scale process with supported bulky ligand metallocene-typecatalysts.

[0012] PCT Publication WO 97/46599 published Dec. 11, 1997 relates tothe use of soluble metallocene catalysts in a gas phase processutilizing soluble metallocene catalysts that are fed into a lean zone ina polymerization reactor to produce stereoregular polymers. This PCTpublication generally mentions that the catalyst feedstream can containantifoulants or antistatic agents such as ATMER 163 (available from ICISpecialty Chemicals, Baltimore, Md.).

[0013] EP-A2-8 11 638 discusses using a metallocene catalyst and anactivating cocatalyst in a polymerization process in the presence of anitrogen containing antistatic agent. This European publication mentionsvarious methods for introducing the antistatic agent, most preferablythe antistatic agent is sprayed into the fluidized bed of the reactor.Another method generally discussed is the adding of an antistatic agentwith the supported or liquid catalyst stream so long as the catalystsare not severely affected or poisoned by the antistatic agent. In theexamples the supported catalysts were slurried in mineral oil prior tobeing introduced to the reactor and in the examples using theunsupported catalysts, the antistatic agent was introduced directly tothe reactor.

[0014] Thus, it would be advantageous to have a polymerization processcapable of operating continuously with enhanced reactor operabilitywhile at the same time producing polymers having improved physicalproperties. It would also be highly advantageous to have a continuouslyoperating polymerization process having more stable catalystproductivities and reduced fouling/sheeting tendencies and increasedduration of operation.

SUMMARY OF THE INVENTION

[0015] This invention provides for an improved method for delivering asupported bulky ligand metallocene-type catalyst system to a reactor foruse in the polymerization of olefin(s).

[0016] The invention more particularly provides for a method fordelivering a supported bulky ligand metallocene-type catalyst system toa gas or slurry phase polymerization reactor utilizing a carriersolution comprising an antistatic agent and a liquid diluent, whereinthe carrier solution serves to flush the supported bulky ligandmetallocene-type catalyst system into the reactor.

[0017] In another embodiment, the invention provides for a gas or slurryphase process for polymerizing olefin(s) in a reactor in the presence ofa supported bulky ligand metallocene-type catalyst system, wherein thesupported bulky ligand metallocene-type catalyst system is introduced tothe reactor by a carrier solution, the carrier solution comprising anantistatic agent and a liquid diluent.

[0018] In yet another embodiment, the invention provides for apolymerization catalyst composition of a preformed and substantiallydried supported bulky ligand metallocene-type catalyst system and acarrier solution comprising an antistatic agent and a liquid diluent.The invention also provides for the use of the polymerization catalystcomposition in a polymerization process of olefin(s).

[0019] In another embodiment, the invention provides for a new andimproved catalyst feeder for use in combination with a reactor vesselhaving within the reactor vessel a reaction zone, the catalyst feedercomprising a catalyst vessel for containing a polymerization catalyst,the catalyst vessel connected to a catalyst injection tube fordelivering the polymerization catalyst to the reaction zone, thecatalyst injection tube being disposed within a support tube thatprotrudes through the polymerization reactor wall into the reactionzone, and the catalyst feeder further comprising a means for contactingthe polymerization catalyst with a carrier solution comprising anantistatic agent and a liquid diluent prior to the polymerizationcatalyst entering the reaction zone.

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The foregoing aspects, features and advantages of the inventionwill become clearer and more fully understood when the followingdetailed description is read in conjunction with the accompanyingdrawing, in which:

[0021]FIG. 1 illustrates the catalyst feeder of the invention.

DETAILED DESCRIPTION OF THE INVENTION Introduction

[0022] The invention is directed toward an improved method fordelivering to a polymerization reactor a supported bulky ligandmetallocene-type catalyst system. It has been discovered that the methodby which the supported bulky ligand metallocene-type catalyst isintroduced into a reactor can affect the operability of a polymerizationprocess. Much of the art discusses the introduction of an antistaticagent directly to the reactor to reduce static build-up, reduce foulingand sheeting, and eliminate hot spots throughout the reactor system.Others in the art have discussed methods of producing a supportedcatalyst system with an antistatic agent as part of the method of makingthe supported catalyst system. These methods however do not completelyeliminate sheeting or plugging of the catalyst feed tubes, particularlywhen using highly active bulky ligand metallocene-type catalyst systems.The surprising benefits attributable to the method of delivering asupported bulky ligand metallocene-type catalyst system has beendiscovered.

[0023] It has been discovered that the delivery of a supportedmetallocene-type catalyst system using an inert gas, by itself, such asnitrogen can result in operability problems, such as fouling at the tipof a catalyst injection tube. This type of tip fouling results in a poorand uneven catalyst flow rate into the reactor, reduced catalystefficiency and reduced particle morphology. As a result of this form offouling, during a polymerization process, the catalyst injection tubemust be cleared or replaced. Either partial or complete pluggage of thecatalyst injection tube requires constant monitoring of the condition ofthe catalyst injection tube. Often this type of fouling will result in apolymer agglomeration at the tip of the catalyst injection tuberesulting in partial or complete blockage. Also, the agglomeration isdifficult in many instances to dislodge, and even if cleared, theagglomeration has no where else to go but into the reactor and mayfurther hinder the operability of the process.

[0024] It has been surprisingly discovered that utilizing a carriersolution of an antistatic agent and a liquid diluent in which apreformed supported bulky ligand metallocene-type catalyst system iscontacted, results in better process operability. In fact, delivery ofthe supported bulky ligand metallocene-type catalyst system is moreuniform, catalyst efficiency is improved, and particle morphology isbetter. Even more importantly, plugging of the catalyst injection tubeis substantially reduced or eliminated. In commercial operations wherethe supported catalyst system is introduced continuously, this pluggingphenomenon is easily recognizable. However, plugging is not a majorconcern in small or lab-scale reactors because typically catalyst isintroduced as a one-time slug. The method for delivery of the inventionis particularly well suited to bulky ligand metallocene-type catalystcompounds that tend to be highly incorporating of comonomer. Also, itwas suprising that using the method of the invention fractional meltindex and higher density polymers may be produced in a polymerizationprocess having improved operability.

Catalyst Components and Catalyst Systems

[0025] Generally, bulky ligand transition metallocene-type catalystcompounds include half and full sandwhich compounds having one or morebulky ligands including cyclopentadienyl structures or other similarfunctioning structure such as pentadiene, cyclooctatetraendiyl andimides. The bulky ligands are capable of η-5 bonding to a transitionmetal atom, for example from Group 4, 5 and 6 of the Periodic Table ofElements. Non-limiting examples of catalyst components and catalystsystems are discussed in for example, U.S. Pat. Nos. 4,530,914,4,871,705, 4,937,299, 5,124,418, 5,017,714, 5,120,867, 5,210,352,5,278,264, 5,278,119, 5,304,614, 5,324,800, 5,347,025, 5,350,723,5,391,790, 5,391,789, 5,399,636, 5,539,124, 5,455,366, 5,534,473,5,684,098, 5,693,730, 5,698,634, 5,710,297, 5,712,354, 5,714,427,5,714,555, 5,728,641, 5,728,839 and 5,753,577 all of which are hereinfully incorporated by reference. Also, the disclosures of Europeanpublications EP-A-0 591 756, EP-A-0 520 732, EP-A-0 420 436, EP-B1 0 485822, EP-B1 0 485 823, EP-A2-0 743 324 and EP-B1 0 518 092 and PCTpublications WO 91/04257, WO 92/00333, WO 93/08221, WO 93/08199, WO94/01471, WO 96/20233, WO 97/15582, WO 97/19959, WO 97/46567, WO98/01455 and WO 98/06759 are all herein fully incorporated by referencefor purposes of describing typical bulky ligand transition metalmetallocene-type catalyst compounds and catalyst systems.

Bulky Ligand Metallocene-Type Catalyst Compounds

[0026] Typical bulky ligand metallocene-type catalyst compounds of theinvention are represented by the formula:

L^(A)L^(B)MQ  (I)

[0027] where M is a metal from the Periodic Table of the Elements andmay be a Group 3 to 10 metal, preferably, a Group 4, 5 or 6 transitionmetal or a metal from the lanthanide or actinide series, more preferablyM is a transition metal from Group 4, even more preferably zirconium,hafnium or titanium. L^(A) and L^(B) are bulky ligands that includecyclopentadienyl derived ligands or substituted cyclopentadienyl derivedor heteroatom substituted cyclopentadienyl derived ligands orhydrocarbyl substituted cyclopentadienyl derived ligands or moietiessuch as indenyl ligands, a benzindenyl ligands or a fluorenyl ligands,an octahydrofluorenyl ligands, a cyclooctatetraendiyl ligands, an azenylligands and the like, including hydrogenated versions thereof. Also,L^(A) and L^(B) may be any other ligand structure capable of η-5 bondingto M, for example L^(A) and L^(B) may comprises one or more heteroatoms,for example, nitrogen, silicon, germanium, and phosphorous, incombination with carbon atoms to form a cyclic structure, for example aheterocyclopentadienyl ancillary ligand. Further, each of L^(A) andL^(B) may also be other types of bulky ligands including but not limitedto bulky amides, phosphides, alkoxides, aryloxides, imides, carbolides,borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Each L^(A) and L^(B) may be the same or differenttype of bulky ligand that is π-bonded to M.

[0028] Each L^(A) and L^(B) may be substituted with a combination ofsubstituent groups R. Non-limiting examples of substituent groups Rinclude hydrogen or linear, branched, alkyl radicals or cyclic alkyl,alkenyl, alkynl or aryl radicals or combination thereof having from 1 to30 carbon atoms or other substituents having up to 50 non-hydrogen atomsthat can also be substituted. Non-limiting examples of alkylsubstituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl,cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, includingall their isomers, for example tertiary butyl, iso propyl etc. Otherhydrocarbyl radicals include fluoromethyl, fluroethyl, difluroethyl,iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substitutedorganometalloid radicals including trimethylsilyl, trimethylgermyl,methyldiethylsilyl and the like; and halocarbyl-substitutedorganometalloid radicals including tris(trifluoromethyl)silyl,methyl-bis (difluoromethyl)silyl, bromomethyldimethylgermyl and thelike; and disubstitiuted boron radicals including dimethylboron forexample; and disubstituted pnictogen radicals including dimethylamine,dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogenradicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide,ethylsulfide. Non-hydrogen substituents R include the atoms carbon,silicon, nitrogen, oxygen, tin, germanium and the like including olefinssuch as but not limited to olefinically unsaturated substituentsincluding vinyl-terminated ligands, for example but-3-enyl or hexene-1.Also, two adjacent R groups are joined to form a ring structure havingfrom 4 to 20 atoms selected from carbon, nitrogen, oxygen, phosphorous,silicon, germanium, boron or a combination thereof.

[0029] Other ligands may be bonded to the transition metal, such as aleaving group Q. Q may be an independently monoanionic labile ligandshaving a sigma-bond to M. Non-limiting examples of Q include weak basessuch as amines, phosphines, ether, carboxylates, dienes, hydrocarbylradicals having from 1 to 20 carbon atoms, hydrides or halogens and thelike. Other examples of Q radicals include those substituents for R asdescribed above and including cyclohexyl, heptyl, tolyl, trifluromethyl,tetramethylene and pentamethylene, methylidene, methyoxy, ethyoxy,propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphideradicals and the like.

[0030] In addition, bulky ligand metallocene-type catalyst compounds ofthe invention are those where L^(A) and L^(B) are bridged to each otherby a bridging group, A. Non-limiting examples of bridging group Ainclude bridging radicals of at least one Group 14 atom, such as but notlimited to carbon, oxygen, nitrogen, silicon, germanium and tin,preferably carbon, silicon and germanium, most preferably silicon. Othernon-limiting examples of bridging groups A include dimethylsilyl,diethylsilyl, methylethylsilyl, trifluoromethylbutylsilyl,bis(trifluoromethyl)silyl, di-n-butylsilyl, silylcyclobutyl,di-i-propylsilyl, di-cyclohexylsilyl, di-phenylsilyl,cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di-t-butylphenylsilyl,di(p-tolyl)silyl, dimethylgermyl, diethylgermyl, methylene,dimethylmethylene, diphenylmethylene, ethylene, 1-2-dimethylethylene,1,2-diphenylethylene, 1,1,2,2-tetramethylethylene,dimethylmethylenedimethylsilyl, methylenediphenylgermyl, methylamine,phenylamine, cyclohexylamine, methylphosphine, phenylphosphine,cyclohexylphosphine and the like.

[0031] In one embodiment, the bulky ligand metallocene-type catalystcompound of the invention is represented by the formula:

(C₅H_(4-d)R_(d)) A_(x) (C₅H_(4-d)R_(d)) M Qg-₂  (II)

[0032] wherein M is a Group 4, 5, 6 transition metal, (C₅H_(4-d)R_(d))is an unsubstituted or substituted cyclopentadienyl derived bulky ligandbonded to M, each R, which can be the same or different, is hydrogen ora substituent group containing up to 50 non-hydrogen atoms orsubstituted or unsubstituted hydrocarbyl having from 1 to 30 carbonatoms or combinations thereof, or two or more carbon atoms are joinedtogether to form a part of a substituted or unsubstituted ring or ringsystem having 4 to 30 carbon atoms, A is one or more of, or acombination of carbon, germanium, silicon, tin, phosphorous or nitrogenatom containing radical bridging two (C₅H_(4-d)R_(d)) rings; moreparticularly, non-limiting examples of A may be represented by R′₂C,R′₂2Si, R′₂Si R′₂Si, R′₂Si R′₂C, R′₂Ge, R′₂Ge, R′₂Si R′₂Ge, R′₂GeR R′₂C,R′N, R′P, R′₂C R′N, R′₂C R′P, R′₂Si R′N, R′₂Si R′P, R′₂GeR′N, R′₂Ge R′P,where R′ is independently, a radical group which is hydride, C₁₋₃₀hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, hydrocarbyl-substituted organometalloid,halocarbyl-substituted organometalloid, disubstituted boron,disubstituted pnictogen, substituted chalcogen, or halogen; each Q whichcan be the same or different is a hydride, substituted or unsubstituted,linear, cyclic or branched, hydrocarbyl having from 1 to 30 carbonatoms, halogen, alkoxides, aryloxides, arnides, phosphides, or any otherunivalent anionic ligand or combination thereof; also, two Q's togethermay form an alkylidene ligand or cyclometallated hydrocarbyl ligand orother divalent anionic chelating ligand, where g is an integercorresponding to the formal oxidation state of M, and d is an integerselected from the 0, 1, 2, 3 or 4 and denoting the degree ofsubstitution and x is an integer from 0 to 1.

[0033] In one embodiment, the bulky ligand metallocene-type compoundsare those where the R substituents on the bulky ligands L^(A), L^(B),(C₅H_(4-d)R_(d)) of formulas (I) and (II) are substituted with the sameor different number of substituents on each of the bulky ligands.

[0034] Other metallocene-type catalysts useful in the invention includemono-cyclopentadienyl heteroatom containing metallocene-type compounds.These types of catalyst systems are described in, for example, PCTpublication WO 92/00333, WO 94/07928, WO 91/04257, WO 94/03506,WO96/00244 and WO 97/15602 and U.S. Pat. Nos. 5,057,475, 5,096,867,5,055,438, 5,198,401, 5,227,440 and 5,264,405 and European publicationEP-A-0 420 436, all of which are herein fully incorporated by reference.Other catalysts useful in the invention may include those described inU.S. Pat. Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022,5,276,208, 5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401 and5,723,398 and PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO98/11144 and European publications EP-A-0 578 838, EP-A-0 638 595,EP-B-0 513 380 and EP-A1-0 816 372, all of which are herein fullyincorporated by reference.

[0035] In another embodiment of this invention the monocyclopentadienylmetallocene-type catalyst compounds useful in the invention arerepresented by the formula:

[0036] wherein M is Ti, Zr or Hf; (C₅H_(5-y-x)R_(x)) is acyclopentadienyl ring which is substituted with from 0 to 5 substituentgroups R, “x” is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution,and each substituent group R is, independently, a radical selected froma group consisting of C₁-C₂₀ hydrocarbyl radicals, substituted C₁-C₂₀hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by ahalogen atom, C₁-C₂₀ hydrocarbyl-substituted metalloid radicals whereinthe metalloid is selected from the Group 14 of the Periodic Table ofElements, and halogen radicals or (C₅H_(5-y-x)R_(x)) is acyclopentadienyl ring in which two adjacent R-groups are joined formingC₄-C₂₀ ring to give a saturated or unsaturated polycycliccyclopentadienyl ligand such as indenyl, tetrahydroindenyl, fluorenyl oroctahydrofluorenyl;

[0037] (JR′_(z-1-y)) is a heteroatom ligand in which J is an elementwith a coordination number of three from Group 15 or an element with acoordination number of two from Group 16 of the Periodic Table ofElements, preferably nitrogen, phosphorus, oxygen or sulfur withnitrogen being preferred, and each R′ is, independently a radicalselected from a group consisting of C₁-C₂₀ hydrocarbyl radicals whereinone or more hydrogen atoms is replaced by a halogen atom, y is 0 or 1,and “z” is the coordination number of the element J;

[0038] each Q is, independently any univalent anionic ligand such ashalogen, hydride, or substituted or unsubstituted C₁-C₃₀ hydrocarbyl,alkoxide, aryloxide, amide or phosphide, provided that two Q may be analkylidene, a cyclometallated hydrocarbyl or any other divalent anionicchelating ligand; and n may be 0,1 or 2;

[0039] A is a covalent bridging group containing a Group 15 or 14element such as, but not limited to, a dialkyl, alkylaryl or diarylsilicon or germanium radical, alkyl or aryl phosphine or amine radical,or a hydrocarbyl radical such as methylene, ethylene and the like;

[0040] L′ is a Lewis base such as diethylether, tetraethylammoniumchloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine,n-butylamine, and the like; and w is a number from 0 to 3. Additionally,L′ may be bonded to any of R, R′ or Q and n is 0, 1, 2 or 3.

[0041] In another embodiment, the bulky ligand type metallocene-typecatalyst compound is a complex of a transition metal, a substituted orunsubstituted pi-bonded ligand, and one or more heteroallyl moieties,such as those described in U.S. Pat. Nos. 5,527,752 and 5,747,406 bothof which are herein fully incorporated by reference. Preferably, thebulky ligand type metallocene-type catalyst compound, themonocycloalkadienyl catalyst compound, may be represented by one of thefollowing formulas:

[0042] wherein M is a transition metal from Group 4, 5 or 6, preferablytitanium zirconium or hafnium, most preferably zirconium or hafnium; Lis a substituted or unsubstituted, pi-bonded ligand coordinated to M,preferably L is a cycloalkadienyl bulky ligand, for examplecyclopentadienyl, indenyl or fluorenyl bulky ligands, optionally withone or more hydrocarbyl substituent groups having from 1 to 20 carbonatoms; each Q is independently selected from the group consisting of—O—, —NR—, —CR₂— and — S—, preferably oxygen; Y is either C or S,preferably carbon; Z is selected from the group consisting of —OR, —NR₂,—CR₃, —SR, —SiR₃, —PR₂, —H, and substituted or unsubstituted arylgroups, with the proviso that when Q is — NR— then Z is selected fromthe group consisting of —OR, —NR₂, —SR, —SiR₃, —PR₂ and —H, preferably Zis selected from the group consisting of —OR, — CR₃ and —NR₂; n is 1 or2, preferably 1; A is a univalent anionic group when n is 2 or A is adivalent anionic group when n is 1, preferably A is a carbamate,carboxylate, or other heteroallyl moiety described by the Q, Y and Zcombination; and each R is independently a group containing carbon,silicon, nitrogen, oxygen, and/or phosphorus where one or more R groupsmay be attached to the L substituent, preferably R is a hydrocarbongroup containing from 1 to 20 carbon atoms, most preferably an alkyl,cycloalkyl, or an aryl group and one or more may be attached to the Lsubstituent; and T is a bridging group selected from the groupconsisting of alkylene and arylene groups containing from 1 to 10 carbonatoms optionally substituted with carbon or heteroatoms, germanium,silicone and alkyl phosphine; and m is 2 to 7, preferably 2 to 6, mostpreferably 2 or 3.

[0043] In formulas (IV) and (V), the supportive substituent formed by Q,Y and Z is a unicharged polydentate ligand exerting electronic effectsdue to its high polarizability, similar to the cyclopentadienyl ligand.In the most preferred embodiments of this invention, the disubstitutedcarbamates and the carboxylates are employed. Non-limiting examples ofmonocycloalkadienyl catalyst compounds include indenyl zirconiumtris(diethylcarbamate), indenyl zirconium tris(trimethylacetate),indenyl zirconium tris(p-toluate), indenyl zirconium tris(benzoate),(1-methylindenyl)zirconium tris(trimethylacetate), (2-methylindenyl)zirconium tris(diethylcarbamate), (methylcyclopentadienyl) zirconiumtris(trimethylacetate), cyclopentadienyl tris(trimethylacetate),tetrahydroindenyl zirconium tris(trimethylacetate), and(pentamethyl-cyclopentadienyl) zirconium tris(benzoate). Preferredexamples are indenyl zirconium tris(diethylcarbamate), indenyl zirconiumtris(trimethylacetate), and (methylcyclopentadienyl) zirconiumtris(trimethylacetate).

[0044] In another embodiment of the invention the bulky ligandmetallocene-type catalyst compounds are those nitrogen containingheterocyclic ligand complexes, also known as transition metal catalystsbased on bidentate ligands containing pyridine or quinoline moieties,such as those described in WO 96/33202 herein incorporated by reference.

[0045] It is contemplated in some embodiments, that the bulky ligands ofthe metallocene-type catalyst compounds of the invention described aboveare asymmetrically substituted in terms of additional substituents ortypes of substituents, and/or unbalanced in terms of the number ofadditional substituents on the bulky ligands or the bulky ligandsthemselves are different. It is also contemplated that in oneembodiment, the metallocene-type catalysts of the invention includetheir structural or optical or enantiomeric isomers and mixturesthereof. In another embodiment the bulky ligand metallocene-typecompounds of the invention may be chiral and/or a bridged bulky ligandmetallocene-type catalyst compound.

[0046] It is also within the scope of this invention that the abovedescribed bulky ligand metallocene-type catalyst compounds can becombined with one or more of the catalyst compounds represented byformula (I), (II), (III), (IV) and (V) with one or more activators oractivation methods described below.

Activator and Activation Methods

[0047] The above described bulky ligand metallocene-type catalystcompounds of the invention are typically activated in various ways toyield catalyst compounds having a vacant coordination site that willcoordinate, insert, and polymerize olefins.

[0048] For the purposes of this patent specification and appendedclaims, the term “activator” is defined to be any compound or componentor method which can activate any of the bulky ligand metallocene-typecatalyst compounds of the invention as described above. Non-limitingactivators, for example may include a Lewis acid or a non-coordinatingionic activator or ionizing activator or any other compound that canconvert a neutral bulky ligand metallocene-type catalyst component to abulky ligand metallocene cation. It is within the scope of thisinvention to use alumoxane or modified alumoxane as an activator, and/orto also use ionizing activators, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) boron or a trisperfluorophenylboron metalloid precursor that would ionize the neutral metallocenecompound.

[0049] There are a variety of methods for preparing alumoxane andmodified alumoxanes, non-limiting examples of which are described inU.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419,4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529,5,693,838, 5,731,253, 5,731,451 5,744,656 and European publicationsEP-A-0 561 476, EP-B 1-0 279 586 and EP-A-0 594-218, and PCT publicationWO 94/10180, all of which are herein fully incorporated by reference.

[0050] Ionizing compounds may contain an active proton, or some othercation associated with but not coordinated to or only looselycoordinated to the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-A-0 426 637, EP-A-500 944,EP-A-0 277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157,5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,387,568, 5,384,299 and5,502,124 and U.S. patent application Ser. No. 08/285,380, filed Aug. 3,1994, all of which are herein fully incorporated by reference.

[0051] Other activators include those described in PCT publication WO98/07515 such as tris (2, 2′, 2″-nonafluorobiphenyl) fluoroaluminate,which publication is fully incorporated herein by reference.Combinations of activators are also contemplated by the invention, forexample, alumoxanes and ionizing activators in combinations, see forexample, PCT publications WO 94/07928 and WO 95/14044 and U.S. Pat. Nos.5,153,157 and 5,453,410 all of which are herein fully incorporated byreference. Also, methods of activation such as using radiation (seeEP-B1-0 615 981 herein incorporated by reference) and the like are alsocontemplated as activating methods for the purposes of rendering theneutral bulky ligand metallocene-type catalyst compound or precursor toa metallocene-type cation capable of polymerizing olefins.

[0052] It is further contemplated by the invention that other catalystscan be combined with the bulky ligand metallocene-type catalystcompounds of the invention. For example, see U.S. Pat. Nos. 4,937,299,4,935,474, 5,281,679, 5,359,015, 5,470,811, and 5,719,241 all of whichare herein fully incorporated herein reference.

[0053] In another embodiment of the invention the bulky ligandmetallocene-type catalyst compounds of the invention may be used incombination with a non-metallocene or traditional Ziegler-Natta catalyst(excludes a cyclopentadienyl containing moiety) or catalyst system, orchromium based catalysts or catalyst systems, non-limiting examples aredescribed in U.S. Pat. Nos. 4,159,965, 4,325,837, 4,701,432, 5,124,418,5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264 and 5,723,399 andPCT Publication WO 96/23010 published Aug. 1, 1996 all of which areherein fully incorporated by reference.

Supporting Methods

[0054] It is also within the scope of this invention that the abovedescribed bulky ligand metallocene-type catalyst compounds can becombined with one or more support materials using one of the supportmethods described below. In the preferred embodiment, the bulky ligandmetallocene-type catalyst systems of the invention are in a supportedform, for example deposited on, contacted with, or incorporated within,a support material.

[0055] The terms “support” is any support material, preferably a poroussupport material, for example, talc, inorganic oxides, inorganicchlorides, and magnesium chloride, and resinous support materials suchas polystyrene or a functionalized organic support or crosslinkedorganic support such as polystyrene divinyl benzene polyolefins orpolymeric compounds, or any other organic or inorganic support materialand the like, or mixtures thereof.

[0056] The preferred support materials are inorganic oxide materials,which include those of Groups 2, 3, 4, 5, 13 or 14 metal oxides. In apreferred embodiment, the mixed metallocene-type catalyst supportmaterials include silica, alumina, silica-alumina, and mixtures thereof.Other inorganic oxides that may be employed either alone or incombination with the silica, alumina or silica-alumina, and magnesia,titania, zirconia, montmorillonite and the like or combination thereof,for example, silica-chromium, silica-titania.

[0057] It is preferred that the carrier of the bulky ligandmetallocene-type catalysts of this invention, preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 10 to about 500 μm.More preferably, the surface area is in the range of from about 50 toabout 500 m²/g, pore volume of from about 0.5 to about 3.5 cc/g andaverage particle size of from about 20 to about 200 μm. Most preferablythe surface area range is from about 100 to about 400 m²/g, pore volumefrom about 0.8 to about 3.0 cc/g and average particle size is from about20 to about 100 μm. The average pore size of the carrier of theinvention typically has pore size in the range of from 10 to 1000 Å,preferably 50 to about 500 Å, and most preferably 75 to about 350 Å.

[0058] Examples of supporting the bulky ligand metallocene-type catalystsystems of the invention are described in U.S. Pat. Nos. 4,701,432,4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228, 5,238,892,5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649, 5,466,766,5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835, 5,625,015,5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400, 5,723,402 and5,731,261 and U.S. application Ser. Nos. 271,598 filed Jul. 7, 1994 and788,736 filed Jan. 23, 1997 and PCT publications WO 95/32995, WO95/14044, WO 96/06187 and WO 97/02297 all of which are herein fullyincorporated by reference.

[0059] It has also been discovered that utilizing the catalyst deliverymethod of the invention, smaller particle size support materials may beused. For example, silica having an average particle size from about 10microns to 80 microns. Silica materials of this size are available fromCrosfield, Manchester, England, for example Crosfield ES-70 having anaverage particle size of 40 microns.

[0060] It is contemplated that the bulky ligand metallocene-typecatalyst compounds of the invention may be deposited on the same orseparate supports together with an activator, or the activator may beused in an unsupported form, or may be deposited on a support differentfrom the supported bulky ligand metallocene-type catalyst compounds ofthe invention, or any combination thereof.

[0061] In another embodiment, the bulky ligand metallocene-type catalystcompound of the invention contains a polymer bound ligand as describedin U.S. Pat. No. 5,473,202 which is herein fully incorporated byreference. In one embodiment the bulky ligand metallocene-type catalystsystem of the invention is spray dried as described in U.S. Pat. No.5,648,310 which is fully incorporated herein by reference. In anembodiment the support used with the bulky ligand metallocene-typecatalyst system of the invention is functionalized as described inEuropean publication EP-A-0 802 203, or at least one substituent orleaving group is selected as described in U.S. Pat. No. 5,688,880, bothof which are herein fully incorporated by reference.

[0062] In another embodiment, the invention provides for a supportedbulky ligand metallocene-type catalyst system that includes anantistatic agent or surface modifier in the preparation of the supportedcatalyst system, as described in PCT publication WO 96/11960 which isherein fully incorporated by reference.

[0063] A preferred method for producing the supported bulky ligandmetallocene-type catalyst system of the invention is described below andcan be found in U.S. application Ser. Nos. 265,533, filed Jun. 24, 1994and 265,532, filed Jun. 24, 1994 and PCT publications WO 96/00245 and WO96/00243 both published Jan. 4, 1996, all of which are herein fullyincorporated by reference.

[0064] In a preferred embodiment, the bulky ligand metallocene-typecatalyst compound is slurried in a liquid to form a metallocene solutionand a separate solution is formed containing an activator and a liquid.The liquid can be any compatible solvent or other liquid capable offorming a solution or the like with at least one of the bulky ligandmetallocene-type catalyst compounds of the invention and/or at least oneactivator. In the preferred embodiment the liquid is a cyclic aliphaticor aromatic hydrocarbon, most preferably toluene. The bulky ligandmetallocene-type catalyst compound and activator solutions are mixedtogether and added to a porous support or the porous support is added tothe solutions such that the total volume of the bulky ligandmetallocene-type catalyst compound solution and the activator solutionor the bulky ligand metallocene-type catalyst compound and activatorsolution is less than four times the pore volume of the porous support,more preferably less than three times, even more preferably less thantwo times; preferred ranges being from 1.1 times to 3.5 times range andmost preferably in the 1.2 to 3 times range.

[0065] Procedures for measuring the total pore volume of a poroussupport are well known in the art. Details of one of these procedures isdiscussed in Volume 1, Experimental Methods in Catalytic Research(Academic Press, 1968) (specifically see pages 67-96). This preferredprocedure involves the use of a classical BET apparatus for nitrogenabsorption. Another method well known in the art is described in Innes,Total Porosity and Particle Density of Fluid Catalysts By LiquidTitration, Vol. 28, No. 3, Analytical Chemistry 332-334 (March, 1956).

[0066] The mole ratio of the metal of the activator component to themetal of the bulky ligand metallocene-type catalyst compounds are in therange of ratios between 0.3:1 to 1000: 1, preferably 20:1 to 800: 1, andmost preferably 50:1 to 500:1. Where the activator is an aluminum-freeionizing activator such as those based on the aniontetrakis(pentafluorophenyl)boron, the mole ratio of the metal of theactivator component to the metal component is preferably in the range ofratios between 0.3:1 to 3:1.

[0067] In one embodiment of the process of the invention, olefin(s),preferably C₂ to C₃₀ olefin(s) or alpha-olefin(s), preferably ethyleneor propylene or combinations thereof are prepolymerized in the presenceof the bulky ligand metallocene-type catalyst system of the inventionprior to the main polymerization. The prepolymerization can be carriedout batchwise or continuously in gas, solution or slurry phase includingat elevated pressures. The prepolymerization can take place with anyalpha-olefin monomer or combination and/or in the presence of anymolecular weight controlling agent such as hydrogen. For examples ofprepolymerization procedures, see U.S. Pat. Nos. 4,923,833, 4,921,825,5,283,278 and 5,705,578 and European publication EP-B-0279 863 and PCTPublication WO 97/44371 all of which are herein fully incorporated byreference.

Antistatic Agents

[0068] For the purposes of this patent specification and appended claimsthe term “antistatic agent” is any organic compound containing at leastone electron rich heteroatom from Groups IV, V and/or VI and ahydrocarbyl moiety. Non-limiting examples of typical heteroatoms includesilicon, oxygen, nitrogen, phosphorus, and sulfur. The antistatic agentshould also contain at least one active hydrogen atom attached to theheteroatom. It is preferable that the hydrocarbyl moiety should have amolecular weight sufficient to give it solubility in typical hydrocarbonsolvents, such as, for example a cyclic aliphatic or aromatichydrocarbon, for example toluene.

[0069] The antistatic agent may be represented by the formula,R_(m)XR′_(n), where R is a branched or straight chain hydrocarbyl groupor substituted hydrocarbyl group or groups having one or more carbonatoms, R′ is an alkyl hydroxy group such as —CH₂CH₂OH, X is at least oneheteroatom, which are O, N, P or S atoms or a combination thereof; and nis such that the formula has no net charge.

[0070] Non limiting examples of the following general structures with Rbeing the hydrocarbyl groups are: RNH₂, R₂NH, (R′C(OH)_(n)R″)NH₂,(R′C(OH)_(n)R″)₂NH, RCONH₂, RCONHR, RN(ROH)₂, RCO₂H, RC(O)NROH, RC(S)OH,and R₂PO₂H. These compounds include amines, alcohols, phenols, thiols,silanols, diols, acids, and ethers.

[0071] In another embodiment the antistatic agent of this invention canbe expressed by the formula:

[0072] where R³ is hydrogen or a branched or preferably a straight chainalkyl group having 1 to 50 carbon atoms. R¹ and R² can be the same ordifferent and could be the same as R³ or contain another heteroatom suchas O, N, P or S.

[0073] In another embodiment, the antistatic agent is represented by thefollowing formula for a hydroxy containing alkyl tertiary amine:

[0074] where R¹ can be hydrogen or a (linear or branched) alkyl group offrom 1 to 50 carbon atoms, preferably greater than 12 carbon atoms; R²can be a hydroxy group such a (CH₂)_(x)OH radical where x is an integerfrom 1 to 50, preferably 2 to 25. Non-limiting examples include KemamineAS-990 (available from Witco Chemical Corporation, Houston, Tex.) havingthe formula C₁₈H₃₇N(CH₂CH₂OH)₂ and Kemamine AS-650 (also available fromWitco) having the formula C₁₂H₂₅N(CH₂CH₂OH)₂. Other antistatic agentsinclude bishydroxyethylcocoamine, 2,2-(octadecylamino)bis ethanol,polyoxyethylene alkylamine, butyl stearate, glycerol and SPAN-80(available from ICI Specialties, Wilmington, Del.) having the formula:

(CH₃)(CH₂)₇CHCH(CH₂)₇OCOCH₂(CHOH)₄CH₂OH (sorbitan mono-oleate).

[0075] Quaternary ammonium compounds, hydrocarbyl sulfates or phosphatescan also be used as antistatic agents. Tertiary amines, ethoxylatedamines and polyether compounds are preferable antistatic agents. Theantistatic agents may also be synthetically derived or otherwise.

Method of Delivery

[0076] The supported bulky ligand metallocene-type catalyst compound orcatalyst system is delivered into a polymerization reactor by variousknown methods in the art. For example, U.S. Pat. Nos. 4,543,399, whichis fully incorporated herein by reference, describes a catalyst feedermechanism for introducing a catalyst to a reactor. In an embodiment ofthe invention, the supported metallocene-type catalyst system of theinvention may be fed to a reactor in the catalyst feeder mechanismdescribed in PCT publication WO 97/46599, which is fully incorporatedherein by reference. Other catalyst feeders useful in the inventioninclude slurry-type feeders, rotary and shot feeders, intermittent andcontinuous feeders.

[0077] The supported bulky ligand metallocene-type catalyst compound orcatalyst system is delivered into a polymerization reactor by at leastone carrier solution. In another embodiment, the supported bulk ligandmetallocene-type catalyst compound or catalyst system is contacted withat least one carrier solution prior to being introduced into thepolymerization zone in a polymerization reactor.

[0078] In one embodiment of the invention, the supported bulky ligandmetallocene-type catalyst system is delivered into the polymerizationreactor intermittently or continuously by a carrier solution, preferablythe carrier solution is introduced continuously with the supportedcatalyst system.

[0079] In another embodiment of the invention, when transitioning from afirst catalyst to a second catalyst, preferably where the first andsecond catalyst is a bulky ligand metallocene-type catalyst compound,more preferably where the second catalyst is a bridged, bulky ligandmetallocene-type catalyst compound, it would be preferable during thetransition to use a carrier solution to deliver the second catalystcompound to the polymerization reactor.

[0080] In another embodiment of the invention, when starting up apolymerization process the supported bulky ligand metallocene-typecatalyst system is initially delivered to the polymerization zone in thereactor by a carrier solution. Once the polymerization process hasstabilized, preferably where the process is producing one or more of thedesired product (density and/or melt index), the desired production rateand/or the desired catalyst productivity, the supported bulky ligandmetallocene-type catalyst system is then introduced to the reactorwithout a carrier solution, for example with an inert gas such asnitrogen.

[0081] The carrier solution includes at least one antistatic agent,examples of which are described above, and a liquid diluent. The liquiddiluent may be any liquid capable of maintaining the antistatic agent insubstantially, preferably completely, a dissolved state. Examples ofliquid diluents include one or more olefin(s) or non-polymerizablehydrocarbons. Non-limiting examples of olefin(s) include those havingfrom 2 to 20 carbon atoms, such as ethylene, propylene, butene-1,4-methyl-pentene-1, hexene-1 and octene-1. Non-limiting examples ofliquid diluents include saturated or unsaturated hydrocarbons. Examplesof suitable liquid diluents are readily volatile liquid hydrocarbons,which may be selected from saturated hydrocarbons containing from 2 to 8carbon atoms. Some suitable saturated hydrocarbons are propane,n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane,isohexane, and other saturated C₆ hydrocarbons, n-heptane, n-octane andother saturated C₇ and C₈ hydrocarbons or mixtures thereof. Thepreferred hydrocarbons are C₄ and C₆ saturated hydrocarbons. It iscontemplate that other liquid diluents may include cyclic aliphatic oraromatic hydrocarbon, for example toluene. However, one in the art wouldappreciate using a liquid diluent having no or little effect on theperformance of the catalyst.

[0082] It is also within the scope of the invention that the carriersolution, in an embodiment, may include an amount of other componentssuch as olefins, diolefins or mixtures thereof.

[0083] It is also contemplated that a gas such as nitrogen, ethylene orpropylene or the like, preferably an inert gas such as nitrogen may beused in combination with the carrier solution of the invention.

[0084] In one embodiment, the carrier solution has in the range of fromabout 0.01 to about 20 weight percent of an antistatic agent based onthe total weight of the carrier solution, more preferably in the rangeof from 0.01 to 10 weight percent, still more preferably in the range offrom 0.1 to about 5 weight percent, and most preferably in the range offrom about 0.1 to about 3 weight percent.

[0085] It the most preferred embodiment it is best to maintain thecarrier solution at a temperature sufficient to keep the antistaticagent in solution, in a dissolved or substantially dissolved state.Thus, in one embodiment, it is preferred to maintain the carriersolution at above 50° F. (10° C.), preferably greater than 60° F. (16°C.). However, one skilled in the art would recognize that it isimportant not to exceed a temperature that would adversely affectcatalyst performance.

[0086] In one embodiment the supported bulky ligand metallocene-typecatalyst system, preferably where the supported bulky ligandmetallocene-type catalyst system is preformed and/or in a dry state, isslurried with a carrier solution prior its introduction into thereactor.

[0087] In another embodiment, the carrier solution contains a sufficientamount of an antistatic agent to yield in the range of from 2 to 100 ppmof the antistatic agent based on the bed weight in the reactor, morepreferably in the range of from about 5 to 30 ppm, and most preferablyin the range of from about 5 to about 20 ppm.

[0088] In another embodiment, the carrier solution has an amount of anantistatic agent such that the polymer produced by the process of theinvention contains less than 10 ppm antistatic agent, preferably lessthan 8 ppm.

[0089] In one embodiment, the carrier solution is present with thesupported bulky ligand metallocene-type catalyst system in an amountsuch that the antistatic agent is from about 1 weight percent to about20 weight percent based on the total weight of the catalyst systemcharged or introduced to the polymerization reactor, preferably from 1weight percent to about 10 weight percent, most preferably from about 3weight percent to 8 weight percent.

[0090] In yet another embodiment, where an antistatic agent isintroduced into the reactor in addition to that which is in the carriersolution, the total amount of antistatic agent used is such that lessthan 20 ppm antistatic agent, preferably less than 10 ppm antistaticagent is contained in the polymer being produced.

[0091] In one preferred embodiment of the invention a catalyst feedermechanism, particularly for use in a gas phase polymerization process isshown in FIG. 1. The catalyst feeder (10) includes a catalyst vessel(12) for containing a polymerization catalyst, preferably in thepresence of an inert gas. The catalyst vessel (12) is connected to acatalyst injection tube (14) within a support tube (16). The catalystinjection tube (14) is for delivering the catalyst into a reactor vessel(18). The support tube (16) protrudes through a reactor wall (20),preferably into a reaction zone (22) within the reactor vessel (18). Thepolymerization catalyst, and in one embodiment the supported bulkyligand metallocene-type catalyst compound, is introduced into thecatalyst injection tube (14) and the liquid diluent is injected into thesupport tube (16) through a line (24). The antistatic agent isintroduced into line (24) through another line (26) that leads into line(24). In one embodiment of the invention the catalyst injection tube(14) is recessed from the end of the support tube (16) to allow contactof the supported catalyst system with a carrier solution (antistaticagent and liquid diluent) prior to the supported catalyst system exitsthe support tube (16). The catalyst injection tube (14) may be recessedabout 2.5 inches (6.4 cm) inward from the end of the support tube (16).The supported catalyst system is introduced with a gas, preferably aninert gas such as nitrogen, to the catalyst injection tube (14) from atypical catalyst vessel (12), particularly a dry catalyst feeder vessel.Non-limiting example of a catalyst feeder is described in U.S. Pat. No.3,779,712, which is fully incorporated herein by reference.

[0092] In another embodiment of the invention a catalyst feedermechanism specifically used in a slurry polymerization process isutilized. Such a catalyst slurry feeder can be adapted similarly to theabove by those of skill in the art.

[0093] In an embodiment of the invention the contact time of thesupported bulky ligand metallocene-type catalyst system with the carriersolution prior to the supported bulky ligand metallocene catalyst systementering the polymerization zone in the reactor is in the range of fromseveral days to less than a few seconds to less than one second,preferably less than 1 hour, more preferably less than 1 minute, evenmore preferably less than 30 seconds, still even more preferably lessthan 15 seconds, and most preferably less than about 2 seconds.

Polymerization Process

[0094] The bulky ligand metallocene-type catalyst compounds and catalystsystems of the invention described above are suitable for use in anypolymerization process. The polymerization process of the inventionincludes a solution, gas or slurry process (including a high pressureprocess) or a combination thereof, more preferably a gas or slurry phaseprocess.

[0095] In an embodiment, this invention is directed toward the solution,slurry or gas phase polymerization or copolymerization reactionsinvolving the polymerization of one or more of the olefin monomer(s)having from 2 to 30 carbon atoms, preferably 2 tol2 carbon atoms, andmore preferably 2 to 8 carbon atoms. The invention is particularly wellsuited to the copolymerization reactions involving the polymerization ofone or more olefin monomers of ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1, decene-1, and cyclic olefins ora combination thereof. Other monomers can include vinyl monomers,diolefins such as dienes, polyenes, norbornene, norbornadiene monomers.Preferably a copolymer of ethylene is produced, where the comonomer isat least one alpha-olefin having from 4 to 15 carbon atoms, preferablyfrom 4 to 12 carbon atoms, and most preferably from 4 to 8 carbon atoms.

[0096] In another embodiment ethylene or propylene is polymerized withat least two different comonomers to form a terpolymer; the preferredcomonomers are a combination of alpha-olefin monomers having 4 to 10carbon atoms, more preferably 4 to 8 carbon atoms, optionally with atleast one diene monomer. The preferred terpolymers include thecombinations such as ethylene/butene-1/hexene-1,ethylene/propylene/butene-1, propylene/ethylene/hexene-1,ethylene/propylene/norbornene and the like.

[0097] In the most preferred embodiment the process of the inventionrelates to the polymerization of ethylene and at least one comonomerhaving from 4 to 8 carbon atoms in the presence of a bulky ligandmetallocene-type catalyst compound and an activator supported on acarrier. Particularly, the comonomers are butene-1, 4-methyl-pentene-1,hexene-1 and octene-1, the most preferred being hexene-1.

[0098] Typically in a gas phase polymerization process a continuouscycle is employed where in one part of the cycle of a reactor system, acycling gas stream, otherwise known as a recycle stream or fluidizingmedium, is heated in the reactor by the heat of polymerization. Thisheat is removed from the recycle composition in another part of thecycle by a cooling system external to the reactor. Generally, in a gasfluidized bed process for producing polymers, a gaseous streamcontaining one or more monomers is continuously cycled through afluidized bed in the presence of a catalyst under reactive conditions.The gaseous stream is withdrawn from the fluidized bed and recycled backinto the reactor. Simultaneously, polymer product is withdrawn from thereactor and fresh monomer is added to replace the polymerized monomer.(See for example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661 and 5,668,228 all of which are fully incorporated herein byreference.)

[0099] The reactor pressure in a gas phase process may vary from about100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the rangeof from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), morepreferably in the range of from about 250 psig (1724 kPa) to about 350psig (2414 kPa).

[0100] The reactor temperature in the gas phase process may vary fromabout 30° C. to about 120° C., preferably from about 60° C. to about115° C., more preferably in the range of from about 70° C. to 110° C.,and most preferably in the range of from about 70° C. to about 95° C.

[0101] Other gas phase processes contemplated by the process of theinvention include those described in U.S. Pat. Nos. 5,627,242, 5,665,818and 5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202and EP-B-634 421 all of which are herein fully incorporated byreference.

[0102] In a preferred embodiment, the reactor utilized in the presentinvention is capable and the process of the invention is producinggreater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr),still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), stilleven more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and mostpreferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than100,000 lbs/hr (45,500 Kg/hr).

[0103] A slurry polymerization process generally uses pressures in therange of from about 1 to about 50 atmospheres and even greater andtemperatures in the range of 0° C. to about 120° C. In a slurrypolymerization, a suspension of solid, particulate polymer is formed ina liquid polymerization diluent medium to which ethylene and comonomersand often hydrogen along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

[0104] A preferred polymerization technique of the invention is referredto as a particle form polymerization, or a slurry process where thetemperature is kept below the temperature at which the polymer goes intosolution. Such technique is well known in the art, and described in forinstance U.S. Pat. No. 3,248,179 which is fully incorporated herein byreference. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. No. 4,613,484, which isherein fully incorporated by reference.

[0105] In an embodiment the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

[0106] Examples of solution processes are described in U.S. Pat. Nos.4,271,060 and 5,589,555, which are fully incorporated herein byreference

[0107] A preferred process of the invention is where the process,preferably a slurry or gas phase process is operated in the absence ofor essentially free of any scavengers, such as triethylaluminum,trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like. This preferredprocess is described in PCT publication WO 96/08520 and U.S. Pat. No.5,712,352, which are herein fully incorporated by reference.

[0108] It has been discovered that a polymerization process utilizingthe catalyst delivery method of the invention may be operated with asmall amount of scavenger with reduced or no effect on processoperability and catalyst performance. Thus, in one embodiment, theinvention provides a process for polymerizing olefin(s) in a reactor inthe presence of a supported bulky ligand metallocene-type catalystsystem and a scavenger to produce a polymer product, wherein thesupported bulky ligand metallocene-type catalyst system is introduced tothe reactor by a carrier solution, the carrier solution comprising anantistatic agent and a liquid diluent.

[0109] It has also been discovered that using the catalyst deliverymethod of the invention it is easier to produce fractional melt indexand higher density polymers. In one embodiment the invention provides aprocess for polymerizing olefin(s) in a reactor in the presence of asupported bulky ligand metallocene-type catalyst system to produce apolymer product, wherein the supported bulky ligand metallocene-typecatalyst system is introduced to the reactor by a carrier solution, andoptionally with an inert gas, the carrier solution comprising anantistatic agent and a liquid diluent and the polymer product has a meltindex less than about 1 dg/min and a density greater than 0.920 g/cc,more preferably the polymer product has a melt index less than about0.75 dg/min and a density greater than 0.925 g/cc.

Polymer Product of the Invention

[0110] The polymers produced by the process of the invention can be usedin a wide variety of products and end-use applications. The polymerstypically have a density in the range of from 0.86 g/cc to 0.97 g/cc,preferably in the range of from 0.88 g/cc to 0.965 g/cc, more preferablyin the range of from 0.900 g/cc to 0.96 g/cc, even more preferably inthe range of from 0.905 g/cc to 0.95 g/cc, yet even more preferably inthe range from 0.910 g/cc to 0.940 g/cc, and most preferably greaterthan 0.915 g/cc, preferably greater than 0.920 g/cc, and most preferablygreater than 0.925 g/cc.

[0111] The polymers of the invention typically have a narrow molecularweight distribution, a weight average molecular weight to number averagemolecular weight (M_(w)/M_(n)) of greater than 1.5 to about 10,particularly greater than 2 to about 8, more preferably greater thanabout 2.2 to less than 8.

[0112] Also, the polymers of the invention typically have a narrowcomposition distribution as measured by Composition Distribution BreadthIndex (CDBI). Further details of determining the CDBI of a copolymer areknown to those skilled in the art. See, for example, PCT PatentApplication WO 93/03093, published Feb. 18, 1993 which is fullyincorporated herein by reference.

[0113] The polymers of the invention in one embodiment have CDBI'sgenerally in the range of greater than 50% to 99%, preferably in therange of 55% to 85%, and more preferably 60% to 80%, even morepreferably greater than 60%, still even more preferably greater than65%.

[0114] The polymers of the present invention in one embodiment have amelt index (MI) or (I₂) as measured by ASTM-D-1238-E in the range from0.01 dg/min to 1000 dg/min, more preferably from about 0.01 dg/min toabout 100 dg/min, even more preferably from about 0.1 dg/min to about 50dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min.

[0115] The polymers of the invention in one embodiment have a melt indexratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of from 10 to lessthan 25, more preferably from about 15 to less than 25.

[0116] The polymers of the invention in a preferred embodiment have amelt index ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of frompreferably greater than 25, more preferably greater than 30, even morepreferably greater that 40, still even more preferably greater than 50and most preferably greater than 65.

[0117] Polymers produced by the process of the invention are useful insuch forming operations as film, sheet, and fiber extrusion andco-extrusion as well as blow molding, injection molding and rotarymolding. Films include blown or cast films formed by coextrusion or bylamination useful as shrink film, cling film, stretch film, sealingfilms, oriented films, snack packaging, heavy duty bags, grocery sacks,baked and frozen food packaging, medical packaging, industrial liners,membranes, etc. in food-contact and non-food contact applications.Fibers include melt spinning, solution spinning and melt blown fiberoperations for use in woven or non-woven form to make filters, diaperfabrics, medical garments, geotextiles, etc. Extruded articles includemedical tubing, wire and cable coatings, geomembranes, and pond liners.Molded articles include single and multi-layered constructions in theform of bottles, tanks, large hollow articles, rigid food containers andtoys, etc.

EXAMPLES

[0118] In order to provide a better understanding of the presentinvention including representative advantages thereof, the followingexamples are offered.

[0119] The properties of the polymer were determined by the followingtest methods:

[0120] Density is measured in accordance with ASTM-D-1238.

[0121] MWD, or polydispersity, is a well-known characteristic ofpolymers. MWD is generally described as the ratio of the weight averagemolecular weight (Mw) to the number average molecular weight (Mn). Theratio of Mw/Mn can be measured by gel permeation chromatographytechniques well known in the art.

Example 1 Preparation of Catalyst A

[0122] Davison grade 948 silica (available from W. R. Grace, DavisonChemical Division, Baltimore, Md.) was dehydrated to 600° C. and used asthe support. The dehydrated silica (850 g) was charged into a 2 gal.reactor and 1060 mil of 30 wt % methylalumoxane (MAO) (available fromAlbemarle Corporation, Baton Rouge, La.) was added with slow agitation.Toluene (2000 ml) was then charged to the reactor and the mixture wasallowed to stir at 150° F. (66° C.) for 4 hours. Following the MAOreaction time, 23 grams of bis-(1,3-methyl-n-butyl cyclopentadienyl)zirconium dichloride was added as a 10 wt % solution in toluene.Reaction time for the bulky ligand metallocene-type catalyst compoundwas 1 hour after which the catalyst system was dried with N₂ under avacuum. Drying time was 3 hours at 150° F. (66° C.) and at a reducedagitator speed of 30 rpm. A total of 1200 grams of dried free flowingcatalyst was isolated.

Example 2 Preparation of Catalyst B

[0123] Into a 10 gal. reactor was added 23 liters of a 15 wt %trimethylaluminum (TMA) solution in heptane. While agitating thesolution, 4.2 kg of silica (Davison 948 grade available from W. R.Grace, Davison Chemical Division, Baltimore, Md.) was added slowly. Thesilica had a measured loss-on-ignition (LOI) of 12.5 wt % (LOI can bemeasured by determining the weight loss of the support material whichhas been held at temperature of about 1000° C. for about 16 hours) andwas added via a dip tube slowly to prevent the reaction temperature fromgoing above 50° F. (10° C.). After all of the silica was added, 94.5 gof the bulky ligand metallocene-type catalyst compound, bis(1,3-methyln-butyl cyclopenta-dienyl) zirconium dichloride, was added as a 10 wt %solution in heptane. The mixture was then allowed to react whilestirring for 1 hour at 150° F. (66° C.) after which the agitation wasstopped; the slurry was allowed to settle and the liquid layer wasremoved by decanting. Four hexane washes were then carried out byintroducing 20 liters of hexane each time, stirring, allowing the solidsto settle and decanting. Drying of the catalyst was then initiated withN₂ flow at 150° F. (66° C.) with slow intermittent agitation until thecatalyst was free flowing.

Example 3 Preparation of Catalyst C

[0124] Into a 2 gallon reactor was charged first with 2.0 liters oftoluene then 1060 g of 30 wt % MAO solution in toluene (available fromAlbemarle), followed by 23.1 g of bis(1,3-methyl-n-butylcyclopentadienyl) zirconium dichloride as a 10% solution in toluene. Themixture was stirred for 60 minutes at room temperature after which 850 gof silica (Davison 948 dehydrated at 600° C.) was added to the liquidwith slow agitation. Stirring speed was increased for approximately 10minutes to insure dispersion of the silica into the liquid and thenappropriate amount of toluene was added to make up a slurry of liquid tosolid having a consistency of 4 cc/g of silica. Mixing was continued for15 minutes at 120 rpm after which 6 g of surface modifier, KemamineAS-990 (available Witco Corporation, Memphis, Tenn.) was dissolved in100 cc of toluene and was added and stirred for 15 minutes. Drying wasthen initiated by vacuum and some N₂ purge at 175° F. (79.4° C.). Whenthe catalyst appeared to be free flowing it was cooled down anddischarged into a nitrogen purged vessel. An approximate yield of 1.0 kgof dry catalyst was obtained.

Polymerization Process

[0125] Into a 2 liter autoclave reactor under a nitrogen purge wascharged with triethylaluminum (TEAL), followed by 60 cc of hexene-1comonomer and 800 cc of isobutane diluent. The content of the reactorwas heated to 80° C. after which, separately, 100 mg of the supportedcatalysts above Catalyst A, B and C was coinjected with a carriersolution having the indicated amount of antistatic agent, KemamineAS-990, as in Table 1. The supported catalyst and carrier solution wasintroduced concurrently with ethylene to make up a total reactorpressure of 325 psig (2240 kPa). The reactor temperature was maintainedat 85° C. and the polymerization was allowed to proceed for 40 min.After 40 minutes the reactor was cooled, ethylene was vented off and thepolymer dried and weighed to obtain the polymer yield. Table 1 providesthe yield and activity data using metallocene catalyst with differentlevels of coinjected Kemamine AS-990. TABLE 1 AS-990 Activity ExampleCatalyst Amount⁽¹⁾ (g/PE/gCat · h) Fouling 4 A None 1725 Medium 5 B 3 wt% 1830 None 6 C 5 wt % 1560 None

[0126] The above examples in Table 1 illustrate the use in combinationof Kemamine AS-990 containing carrier solution with the supported bulkyligand mettalocene-type catalyst systems prior to polymerization. Thedata shows that the carrier solution did not have a negative effect onactivity, and reactor fouling was virtually eliminated.

[0127] Examples 7-12, in Table 2, show the effect on the performance ofCatalyst B when using carrier solutions containing the antistatic agentsKemamine AS-990 and Kenmamine AS-650. TABLE 2 Antistatic Amount ActivityExample Agent (wt %) (g/PE/gCat · h) Fouling 7 None 0 1200 High 8 AS9903 1440 None 9 AS990 3 1545 None 10 None 0 1170 High 11 AS650 2.5 1470None 12 AS650 2.5 1410 None

[0128] The above examples 7-12 of Table 2 illustrate that carriersolutions containing Kemamine AS-650 and Kemamine AS-990 have abeneficial effect on reactor operability.

[0129] Examples 13-17 in Table 3 illustrate the effect of a carriersolution containing Kemamine AS-990 on Catalyst C performance in thepresence of different alkyl scavengers, specifically tri-ethylaluminum(TEAL) and tri-isobutylaluminum (TIBAL). TABLE 3 Antistatic AgentActivity Example Scavenger (wt %) (g/PE/gCat · h) Fouling 13 TEAL 0 1950Low 14 TEAL 2 1695 None 15 TIBAL 0 2640 Medium 16 TIBAL 2 2430 None 17TIBAL 4 2295 None

[0130] The results in Table 3 illustrate that even in the presence ofscavengers such as aluminum alkyls that typically increase the level offouling as seen in Examples 13 and 15, the coinjection of the bulkyligand metallocene-type catalyst system with a carrier solutioneliminates the fouling/sheeting tendency of the supported bulky ligandmetallocene-type catalyst system.

Example 18 Preparation of Catalyst D

[0131] The bulky ligand metallocene-type catalyst compound used in thisExample 18 is a dimethylsilyl-bis(tetrahydroindenyl)zirconium dichloride(Me₂Si(H₄₁Ind)₂ZrCl₂) available from Albemarle Corporation, Baton Rouge,La. The (Me₂Si(H₄Ind)₂ZrCl₂) catalyst compound was prepared on CrosfieldES-70 grade silica which is dehydrated at 600° C. having anapproximately a 1.0 weight percent water content. The Crosfield ES-70grade silica having an Average Particle Size of 40 microns is availablefrom Crosfield, Manchester, England.

[0132] The first step in the manufacture of the supportedmetallocene-type catalyst above involves forming a precursor solution.460 lbs (209 kg) of sparged and dried toluene is added to an agitatedreactor after which 1060 lbs (482 kg) of a 30 weight percentmethylaluminoxane (Albemarle Corp., Baton Rouge, La.) is added. 947 lbs(430 kg) of a 2 weight percent toluene solution of adimethylsilyl-bis(tetrahydroindenyl)zirconium dichloride catalystcompound and 600 lbs (272 kg) of additional toluene are introduced intothe reactor. The precursor solution is then stirred at 80° F. to 100° F.(26.7 to 37.8° C.) for one hour.

[0133] While stirring the precursor solution above, 850 lbs (386 kg) of600° C. dehydrated silica as described above is added slowly to theprecursor solution and the mixture agitated for 30 min. at 80° F. to100° F. (26.7 to 37.8° C.). At the end of the 30 min. agitation of themixture, 240 lbs (109 kg) of a 10 weight percent toluene solution ofAS-990 (N,N-bis(2-hydroxylethyl) octadecylamine ((C₁₈H₃₇N(CH₂CH₂OH)₂)available as Kemamine AS-990 Witco Corporation, Memphis, Tenn., is addedtogether with an additional 110 lbs (50 kg) of a toluene rinse and thereactor contents then mixed for 30 min. while heating to 175° F. (79°C.). After 30 min. vacuum is applied and the catalyst mixture dried at175° F. (79° C.) for about 15 hours to a free flowing powder. The finalcatalyst weight was 1200 lbs (544 kg) and had a Zr wt % of 0.35 and anAl wt % of 12.0.

Polymerization Process

[0134] The catalyst system of Examples 18 was then tested in acontinuous gas phase fluidized bed reactor which comprised a nominal 18inch, schedule 60 reactor having an internal diameter of 16.5 inches.The fluidized bed is made up of polymer granules. The gaseous feedstreams of ethylene and hydrogen together with liquid comonomer weremixed together in a mixing tee arrangement and introduced below thereactor bed into the recycle gas line. Hexene-1 was used as thecomonomer. The individual flow rates of ethylene, hydrogen and comonomerwere controlled to maintain fixed composition targets. The ethyleneconcentration was controlled to maintain a constant ethylene partialpressure. The hydrogen was controlled to maintain a constant hydrogen toethylene mole ratio. The concentration of all the gases were measured byan on-line gas chromatograph to ensure relatively constant compositionin the recycle gas stream. The solid supported bulky ligandmetallocene-type catalyst system was injected directly into thefluidized bed using purified nitrogen at 1.5 lbs/hr (0.68 kg/hr).Additionally, a carrier solution, a 2000 ppm Kemamine AS-990 solution inhexane, was fed into the catalyst addition probe (catalyst injectiontube) in a location close to the reactor inlet and in another locationfurther back from the reactor inlet. In one case, a small hexane (1.5lbs/hr(0.68 Kg/hr)) and nitrogen (3 lbs/hr(1.36 Kg/hr)) flow weremaintained to flush the catalyst through the ⅛ inch (0.32 cm) probe. Inanother case, only the nitrogen was added in addition to the KemamineAS-990 solution fed to the catalyst probe and the rate of nitrogen waslimited to 1.5 lbs/hr (0.68 Kg/hr). The probe location was varied fromthe standard location which is approximately 26 inches (66 cm) above theproduct discharge port to a site approximately 40 inches (102 cm) abovethe product discharge port. (See FIG. 1) The reacting bed of growingpolymer particles is maintained in a fluidized state by the continuousflow of the make up feed and recycle gas through the reaction zone. Asuperficial gas velocity of 1-3 ft/sec (30.5 cm/sec to 91.4 cm/sec) wasused to achieve this. The reactor was operated at a total pressure of300 psig (2069 kPa) and a superficial gas velocity of 2.25 ft/sec (68.6cm/sec) was used to achieve fluidization of the granules. To maintain aconstant reactor temperature, the temperature of the recycle gas iscontinuously adjusted up or down to accommodate any changes in the rateof heat generation due to the polymerization. The fluidized bed wasmaintained at a constant height by withdrawing a portion of the bed at arate equal to the rate of formation of particulate product. The productis removed semi-continuously via a series of valves into a fixed volumechamber, which is simultaneously vented back to the reactor. This allowsfor highly efficient removal of the product, while at the same timerecycling a large portion of the unreacted gases back to the reactor.This product is purged to remove entrained hydrocarbons and treated witha small stream of humidified nitrogen to deactivate any trace quantitiesof residual catalyst.

[0135] The polymerization conditions for polymerization utilizing thecatalyst system of Example 18 and results are set forth in Table 4below. The carrier solution, Kemamine AS-990 was fed as a 2000 ppmsolution in hexane. The Kemamine AS-990 containing solution was fedusing a delivery meter into the catalyst probe which had no annularflush. Kemamine AS-990 flow was regulated to 300 cc/hr and then raisedto 400 cc/hr during the test. The resulting concentration of KemamineAS-990 on a catalyst basis was 3.8 wt % Kemamine AS-990 g/g solidcatalyst. On a polymer basis, this was 8 ppm on a gram Kemamine AS-990/gpolymer basis. The location to which carrier solution, the KemamineAS-990 and hexane, was added to the catalyst probe is approximately 4 ft(122 cm) from the reactor. TABLE 4 Examples Example 18 Catalyst CatalystD Temperature (° F.) (° C.) 185 (85) Pressure (psi) (kPa) 300 (2069) C₂Partial Pressure (psia) (kPa) 205 (1414) Ethylene (mole %)  70 Hydrogen(mole ppm) 765 Hydrogen/Ethylene Conc. ratio  10.93 Hexene (mole %) 0.63 Hexene/Ethylene Conc. ratio  0.009 Bed Weight (lbs) (Kg) 600 (273)Residence Time (hrs)  3.7 Gas Velocity (ft/sec) (cm/sec)  2.25 (68.6)Production Rate (lbs/hr) (Kg/Hr) 160 (72.7) Bulk Density (g/cc)  0.48

[0136] TABLE 6 EXAMPLE 19 20 21 22 Start Date 11/6  11/10 1/10 1/16 EndDate 11/18 11/17 1/15 1/16 BTO's 73 39 30.4 2.7 Catalyst D D D D Cat.Activity 6300 6100 4995 4830 (lbs PE/lb cat) MI (dg/min) 1.94 1.99 1.421.47 Density (g/cc) 0.9197 0.9210 0.9194 0.9188 Resin bulk 0.48 0.480.46 0.48 density (g/cc) AS-990 Carrier Yes Yes Yes No solution

[0137] Examples 19 and 20 of Table 6 using the delivery method of theinvention resulted in extended polymerization runs of 73 and 39 bedturnovers, respectively. Examples 21 and 22 was one continuous run inthe same reactor. As you can see from the data using the method ofdelivery of the invention with Catalyst D in this example resulted inabout 30 bed turnovers (Example 21) and when using the same catalyst atsimilar process conditions without coinjection of a carrier solution,after only about 2.7 bed turnovers the reactor had to be shut-down dueto fouling and sheeting (Example 22).

[0138] While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, it is contemplated that anantistatic agent can be added to reactor in addition to being used in acarrier solution. It is also contemplated that the delivery method ofthe invention can be used in a series reactor process. The deliverymethod and catalyst feeder may be used with conventional Ziegler-Nattaor Phillips-type catalysts in gas phase or slurry phase. For thisreason, then, reference should be made solely to the appended claims forpurposes of determining the true scope of the present invention.

We claim:
 1. A method for delivering a supported bulky ligandmetallocene-type catalyst system to a gas or slurry phase polymerizationreactor utilizing a carrier solution comprising an antistatic agent anda liquid diluent, wherein the carrier solution serves to flush thesupported bulky ligand metallocene-type catalyst system into thereactor.
 2. The method of claim 1 wherein the antistatic agent isrepresented by the formula, R_(m)XR′_(n), where R is a branched orstraight chain hydrocarbyl group or substituted hydrocarbyl group orgroups having one or more carbon atoms, R′ is an alkyl hydroxy group, Xis at least one heteroatom; and n is such that the formula has no netcharge.
 3. The method of claim 1 wherein the antistatic agent is ahydroxy containing alkyl tertiary amine.
 4. The method of claim 1wherein the carrier solution is flushed intermittently with thesupported bulky ligand metallocene-type catalyst system into thereactor.
 5. The method of claim 1 wherein the liquid diluent is one ormore of the group consisting of an olefin having from 2 to 20 carbonatoms and a non-polymerizable saturated or unsaturated hydrocarbon. 6.The method of claim 1 wherein the carrier solution and a gas serve toflush the supported bulky ligand metallocene-type catalyst system intothe reactor.
 7. The method of claim 1 wherein the carrier solutioncomprises about 0.1 to 5 weight percent of the antistatic agent based onthe total weight of the carrier solution.
 8. The method of claim 1wherein the carrier solution is maintained at a temperature above 50° C.at the time of contact with the supported bulky ligand metallocene-typecatalyst system.
 9. The method of claim 8 wherein the time of contact isless than one minute prior to the supported bulky ligandmetallocene-type catalyst system is flushed into the reactor.
 10. Themethod of claim 1 wherein the antistatic agent in the carrier solutionis present in amount from about 2 to about 10 weight percent based onthe total weight of the supported bulky ligand metallocene-type catalystsystem flushed into the reactor at any given time.
 11. The method ofclaim 1 wherein the carrier solution and the supported bulky ligandmetallocene-type catalyst system is flushed through a catalyst injectiontube into the reactor.
 12. The method of claim 1 wherein the carriersolution and the supported bulky ligand metallocene-type catalyst systemare flushed continuously through a catalyst injection tube into thereactor.
 13. The method of claim 1 wherein the reactor is producinggreater than 500 lbs (227 Kg) of polymer per hour.
 14. The method ofclaim 1 wherein reactor is a gas phase reactor having a fluidized bedhaving a bed weight wherein the carrier solution contains a sufficientamount of an antistatic agent to yield in the range of from 2 to 50 ppmof the antistatic agent based on the bed weight in the reactor.
 15. Agas or slurry phase process for polymerizing olefin(s) in a reactor inthe presence of a supported bulky ligand metallocene-type catalystsystem, wherein the supported bulky ligand metallocene-type catalystsystem is introduced to the reactor by a carrier solution, the carriersolution comprising an antistatic agent and a liquid diluent.
 16. Theprocess of claim 15 wherein the process is a gas phase process and thereactor is a fluidized bed reactor.
 17. The process of claim 10 whereinthe antistatic agent is represented by the formula, R_(m)XR′_(n), whereR is a branched or straight chain hydrocarbyl group or substitutedhydrocarbyl group or groups having one or more carbon atoms, R′ is analkyl hydroxy group, X is at least one heteroatom; and n is such thatthe formula has no net charge.
 18. The process of claim 15 wherein thecarrier solution comprises about 0.1 to 10 weight percent of theantistatic agent based on the total weight of the carrier solution. 19.The process of claim 15 wherein the carrier solution is introduced intothe reactor continuously with the supported bulky ligandmetallocene-type catalyst system through an catalyst injection tube intothe reactor.
 20. The process of claim 15 wherein the carrier solutionand a gas are used to introduce the supported bulky ligandmetallocene-type catalyst system into the reactor.
 21. The process ofclaim 15 wherein the carrier solution and the supported bulky ligandmetallocene-type catalyst system contact each other for less than aboutone minute prior to entering the reactor.
 22. The process of claim 15wherein the process is producing a polymer product having a melt indexless than 1 dg/min and a density greater than 0.920g/cc.
 23. The processof claim 22 wherein the polymer product comprises less than 10 ppm ofthe antistatic agent and the process is producing greater than 500 lbs(227 Kg) of polymer per hour.
 24. The process of claim 15 wherein theprocess further comprises introducing a scavenger to the reactor.
 25. Apolymerization catalyst composition comprising a supported bulky ligandmetallocene-type catalyst system and a carrier solution, the carriersolution comprising an antistatic agent and a liquid diluent.
 26. Thepolymerization catalyst composition of claim 25 wherein the antistaticagent is represented by the formula, R_(m)XR′_(n), where R is a branchedor straight chain hydrocarbyl group or substituted hydrocarbyl group orgroups having one or more carbon atoms, R′ is an alkyl hydroxy group, Xis O, N, P or S atom or a combination thereof; and n is such that theformula has no net charge.
 27. The polymerization catalyst compositionof claim 25 wherein the antistatic agent is a hydroxy containing alkyltertiary amine.
 28. The polymerization catalyst composition of claim 25wherein the carrier solution comprises about 0.1 to 5 weight percent ofthe antistatic agent based on the total weight of the carrier solution.29. The polymerization catalyst composition of claim 25 wherein thesupported bulky ligand metallocene-type catalyst system comprises aninorganic support material having a particle size in the range of from10 microns to 80 microns.
 30. The polymerization catalyst composition ofclaim 25 wherein the antistatic agent is present in amount from about 2to about 10 weight percent based on the total weight of the supportedbulky ligand metallocene-type catalyst system.
 31. The polymerizationcatalyst composition of claim 25 wherein the supported bulky ligandmetallocene-type catalyst system comprises at least one bulky ligandmetallocene-type catalyst compound represented by the formula:(C₅H_(4-d)R_(d)) A_(x) (C₅H_(4-d)R_(d)) M Qg-₂ wherein M is a Group 4,5, 6 transition metal, (C₅H_(4-d)R_(d)) is an unsubstituted orsubstituted cyclopentadienyl derived bulky ligand bonded to M, each R,which can be the same or different, is hydrogen or a substituent groupcontaining up to 50 non-hydrogen atoms or substituted or unsubstitutedhydrocarbyl having from 1 to 30 carbon atoms or combinations thereof, ortwo or more carbon atoms are joined together to form a part of asubstituted or unsubstituted ring or ring system having 4 to 30 carbonatoms, A is one or more of, or a combination of carbon, germanium,silicon, tin, phosphorous or nitrogen atom containing radical bridgingtwo (C₅H_(4-d)R_(d)) rings; each Q which can be the same or different isa hydride, substituted or unsubstituted, linear, cyclic or branched,hydrocarbyl having from 1 to 30 carbon atoms, halogen, alkoxides,aryloxides, amides, phosphides, or any other univalent anionic ligand orcombination thereof; also, two Q's together may form an alkylideneligand or cyclometallated hydrocarbyl ligand or other divalent anionicchelating ligand, where g is an integer corresponding to the formaloxidation state of M, and d is an integer selected from the 0, 1, 2, 3or 4 and denoting the degree of substitution and x is an integer from 0to
 1. 32. The polymerization catalyst composition of claim 31 wherein xis
 1. 33. The polymerization catalyst composition of claim 25 whereinthe supported bulky ligand metallocene-type catalyst system comprisesalumoxane.
 34. The polymerization catalyst composition of claim 25wherein the polymerization catalyst composition is introduced to apolymerization reactor by the carrier solution, and optionally in thepresence of an inert gas.
 35. A continuous gas phase process forpolymerizing monomer(s) in a reactor, said process comprising the stepsof: a) introducing a recycle stream into the reactor, the recycle streamcomprising one or more monomer(s) and; b) introducing a supported bulkyligand transition metal metallocene-type catalyst system contacted witha carrier solution, the carrier solution comprising an antistatic agentand a liquid diluent, into the reactor; c) withdrawing the recyclestream from the reactor; d) cooling the recycle stream; e) introducinginto the reactor additional monomer and additional comonomer to replacethe one or more monomer(s) polymerized; f) reintroducing the recyclestream into the reactor; and g) withdrawing a polymer product from thereactor.
 36. The process of claim 35 wherein the antistatic agent is analkoxylated tertiary amine.
 37. The process of claim 35 wherein thecarrier solution comprises about 0.1 to 5 weight percent of theantistatic agent based on the total weight of the carrier solution. 38.The process of claim 35 wherein the polymer product comprises less than10 ppm of the antistatic agent.
 39. The process of claim 35 wherein theprocess is producing a polymer product having a melt index less than 1dg/min and a density greater than 0.920g/cc.
 40. The process of claim 35wherein the process is producing a polymer product having a melt indexless than 0.75 dg/min and a density greater than 0.925 g/cc.
 41. Theprocess of claim 35 wherein the process further comprises the step ofintroducing a scavenger.
 42. The process of claim 35 wherein the carriersolution and the supported bulky ligand metallocene-type catalyst systemcontact each other for less than about 1 minute prior to beingintroduced to the reactor.
 43. The process of claim 35 wherein thesupported bulky ligand transition metal metallocene-type catalyst systemcontacted and carrier solution are introduced into the reactorintermittently.
 44. The process of claim 35 wherein the supported bulkyligand transition metal metallocene-type catalyst system is introducedinto the reactor with the carrier solution upon start-up or until thedesired catalyst productivity, polymer density or melt index areachieved, thereafter the introduction of the carrier solution is haltedand the supported bulky ligand transition metal metallocene-typecatalyst system is introduced into the reactor by an inert gas.
 45. Theprocess of claim 1 wherein the polymer product is withdrawn at a rategreater than 500 lbs (227 Kg) of polymer product per hour.
 46. Theprocess of claim 35 wherein the supported bulky ligand metallocene-typecatalyst system and the carrier solution are introduced to the reactorthrough a catalyst feeder tube.
 47. The process of claim 35 wherein theprocess is operating where the recycle stream is divided into a gasphase and a liquid phase.
 48. The process of claim 35 wherein thesupported bulky ligand metallocene-type catalyst system is a supportedbridged bulky ligand metallocene-type catalyst system.
 49. The processof claim 35 wherein the time of contact between the supported bulkyligand metallocene-type catalyst system and the carrier solution is lessthan about 2 seconds prior to the supported bulky ligandmetallocene-type catalyst system and carrier solution are introducedinto the reactor.
 50. A catalyst feeder for use in combination with areactor vessel having within the reactor vessel a reaction zone, thecatalyst feeder comprising a catalyst vessel for containing apolymerization catalyst, the catalyst vessel connected to a catalystinjection tube for delivering the polymerization catalyst to thereaction zone, the catalyst injection tube being disposed within asupport tube that protrudes through the reactor vessel wall, and thecatalyst feeder further comprising a means for contacting thepolymerization catalyst with a carrier solution comprising an antistaticagent and a liquid diluent prior to the polymerization catalyst enteringthe reaction zone.
 51. The catalyst feeder of claim 50 wherein the meansfor contacting includes a carrier tube for introducing the carriersolution to the catalyst injection tube.
 52. The catalyst feeder ofclaim 50 wherein the means for contacting is a carrier line forintroducing the carrier solution into the support tube and that thecatalyst injection tube is recessed sufficiently to provide contact ofthe polymerization catalyst with the carrier solution prior to theirentering the reaction zone.
 53. The catalyst feeder of claim 50 whereinthe catalyst feeder further comprises a gas line for introducing a gasinto the catalyst feeder.
 54. The catalyst feeder of claim 53 whereinthe means for contacting is at least two delivery lines, one fordelivering the antistatic agent and one for delivering the liquiddiluent.
 55. The catalyst feeder of claim 54 wherein the at least twodelivery lines enter a mixing vessel where the antistatic agent andliquid diluent are combined to form the carrier solution.
 56. Thecatalyst feeder of claim 54 wherein at least one of the delivery linesis connected to the other resulting in the mixing of the antistaticagent and liquid diluent in at least one of the delivery lines.
 57. Thecatalyst feeder of claim 50 wherein catalyst feeder further comprises ameans for maintaining the carrier solution at a temperature above 50° C.58. The catalyst feeder of claim 50 wherein catalyst feeder furthercomprises a means for introducing the carrier solution into the reactorintermittently.
 59. The catalyst feeder of claim 50 wherein thepolymerization catalyst is a supported bulky ligand metallocene-typecatalyst system and the carrier solution comprising from about 2 to 10weight percent antistatic agent based on the total weight of thesupported bulky ligand metallocene-type catalyst system.
 60. Thecatalyst feeder of claim 50 wherein the reactor vessel is a fluidizedbed gas phase reactor.
 61. A continuous gas phase fluidized bed processfor polymerizing olefins(s) in the presence of a supported bulky ligandmetallocene-type catalyst system in a reactor vessel, the supportedbulky ligand metallocene-type catalyst system contacted with a carriersolution comprising an antistatic agent are introduced into the reactorvessel through a catalyst injection tube, wherein the process comprisesthe step of withdrawing greater than 500 lbs (227 Kg) of a polymerproduct per hour, the polymer product having a melt index less than 1dg/min, a density greater than 0.920 g/cc and containing less than 10ppm of the antistatic agent.
 62. The process of claim 61 wherein thepolymer product has a melt index less than 1 dg/min and a densitygreater than 0.925 g/cc.
 63. The process of claim 62 wherein the processcomprises the step of withdrawing greater than 25,000 lbs (90,900 Kg) ofpolymer product per hour.
 64. The process of claim 61 wherein thepolymer product has an I₂₁/I₂ of greater than 30, and a density greaterthan 0.910 g/cc.
 65. A continuous process for polymerizing olefins(s) inthe presence of a polymerization catalyst composition in a reaction zonewithin a polymerization reactor, the polymerization catalyst compositioncomprising a supported bulky ligand metallocene-type catalyst system anda carrier solution comprising an antistatic agent and a liquid diluent,wherein the supported bulky ligand metallocene-type catalyst systemcontacts the carrier solution for less than one minute prior to thepolymerization catalyst composition entering the reaction zone.
 66. Theprocess of claim 65 wherein the supported bulky ligand metallocene-typecatalyst system contacts the carrier solution for less than 30 secondsprior to the polymerization catalyst composition entering the reactionzone.
 67. The process of claim 65 wherein the supported bulky ligandmetallocene-type catalyst system contacts the carrier solution for lessthan two seconds prior to the polymerization catalyst compositionentering the reaction zone.
 68. The process of claim 65 wherein thesupported bulky ligand metallocene-type catalyst system contacts thecarrier solution intermittently.
 69. The process of claim 65 wherein theprocess is a gas phase process and the polymerization reactor is afluidized bed reactor.
 70. The process of claim 65 wherein thepolymerization catalyst composition enters the reaction zone through acatalyst injection tube and the process is producing greater than 500lbs (227 Kg) of a polymer product per hour.
 71. The process of claim 65wherein the process is producing greater than 1000 lbs (455 Kg) of apolymer product per hour.
 72. The process of claim 65 wherein theprocess is producing greater than 10,000 lbs (4540 Kg) of a polymerproduct per hour.
 73. The process of claim 65 wherein the process isproducing greater than 25,000 lbs (11,300 Kg) of a polymer product perhour.
 74. The process of claim 72 wherein the polymer product has adensity greater than 0.900 g/cc.
 75. The process of claim 73 wherein thepolymer product has a density greater than 0.920 g/cc.
 76. The processof claim 75 wherein the polymer product has a melt index less than 1dg/min.
 77. The process of claim 72 wherein the polymer product has adensity greater than 0.925 g/cc and a melt index less than 0.75 dg/min.78. The process of claim 77 wherein the polymer product has an I₂₁/I₂greater than
 30. 79. The process of claim 73 wherein the polymer producthas a density greater than 0.925 g/cc and the I₂₁/I₂ is greater than 60.80. The process of claim 65 wherein the process is producing greaterthan 50,000 lbs (22,700 Kg) of a polymer product per hour and thepolymer product having a density greater than 0.920 g/cc and a I₂₁/I₂greater than 40.